Investigation of chemical effects on the performance of flow-through dialysis applied to the determination of ionic species

In this paper, the influence of chemical variables on the mass transfer kinetics of ionic species under dynamic conditions in flow-through sandwich-type dialysers is thoroughly investigated. Although the driving force of the mass transport is the existence of a concentration gradient between the two phases separated by a semi-permeable membrane, it has been demonstrated that the chemical composition of both donor and acceptor solutions in terms of concentration and kind of ionic compounds has a significant influence on the mass transfer efficiency. The Donnan effect on passive dialysis and the fast migration of ions concomitantly present with the target species improved the transfer of the analyte ion in the membrane separation process. Thus, for the determination of low molecular weight anions, the addition of cationic species with high transport index, such as oxonium ion, to the donor stream, or multicharged ions (e.g. Al3+) to the recipient stream, enhanced the dialysis yields more than 62% with respect to the use of water as acceptor and sample medium. As a consequence of the dependence of the dialysis rate on the composition of the sample matrix, different diffusate concentrations were encountered for the same input concentration of analyte when prepared in different electrolytic media. In order to balance the chemical potential on the donor side, the ionic strength for both standards and sample solutions should be carefully adjusted via incorporation of a modifier stream in the flow manifold (e.g. 1.0 mol l(-1) KNO3 or 0.5 mol l(-1) H2SO4) as demonstrated in the bulk of the text. Appropriate buffering of the recipient solution was equally effective. Furthermore, these strategies were found suitable to overcome the lack of linearity observed by several researchers in in-line dialytic processes at low concentrations of ionic species caused by polar interactions with the membrane surface. Chloride was selected as a model of target species for assessing the effect of chemical variables on the mass transfer rate in flow-through parallel-plate dialyser units. The spectrophotometric detection scheme for chloride, implemented in a secondary flow configuration, is based on the displacement reaction of thiocyanate from the corresponding mercury salt in the presence of iron(III). (C) 2004 Elsevier B.V. All rights reserved.